Patent US3596316A successfully refreshed from Google Patents.
US4178455A
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Process for preparing aromatic urethanes
Assignee: Mitsui Toatsu Chemicals Inc
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Filing: 1978-07-17
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Granted: 1979-12-11
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Expires: 1998-07-17
Abstract
Abstract In a process for preparing an aromatic urethane which comprises reacting an aromatic nitro compound, an organic compound containing at least one hydroxyl group, and carbon monoxide at elevated temperature and pressure in the presence of a catalytic system composed of a catalyst consisting of a platinum metal, a platinum metal compound, and/or a platinum metal compound-containing compound and a promoter consisting of a Lewis acid and/or a Lewis acid-containing compound, an organic primary amino compound, a urea compound, a biuret compound, an allophanate compound, or a mixture thereof is added to the reaction system whereby the reaction rate is increased and the yield of the desired product is enhanced. For example, 2,4-diethylcarbamatetoluene can be prepared in quantitatively high yield by reacting 2,4-dinitrotoluene, ethanol, carbon monoxide, and a small amount of aminonitrotoluene at elevated temperature and pressure in the presence of palladium chloride and ferrous chloride-pyridine complex.
Inventors
- 👤 Yutaka Hirai
- 👤 Katsuharu Miyata
- 👤 Makoto Aiga
- 👤 Seiji Hasegawa
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 19:48
CPC Classifications
C; C07; C07C; C07C271/00; C07C271/06
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
442 words
In a process for preparing an aromatic urethane which comprises reacting at temperature in the range of 80°-230° C. pressures in the range of 10-1000 Kg/cm 2 G for a time ranging from 5 minutes to 6 hours an aromatic nitro compound, an organic hydroxyl-containing compound having at least one hydroxyl group, and carbon monoxide in the presence of a catalyst selected from the group consisting of platinum, palladium, rhodium or ruthenium metal or a compound thereof and mixtures thereof and a promoter selected from the group consisting of Lewis acids, Lewis acid-containing compounds and mixtures thereof, the improvement which comprises adding to the reaction system at least one compound selected from the group consisting of an organic primary amino compound of the formula R.sub.o NH.sub.2 ( I) where R o represents a linear or branched alkyl group containing from 1 to 16 carbon atoms, a cycloalkyl group of 6 carbon atoms with or without an alkyl substituent containing from 1 to 3 carbon atoms, or an aryl group with or without at least one alkyl substituent containing from 1 to 6 carbon atoms, and these alkyl, cycloalkyl and aryl groups may further have at least one halogen, aryl, alkenyl, cyano, nitro, alkoxy, phenoxy, thioalkoxy, thiophenoxy, carbalkoxy, carbamate, carbamyl, carbaryloxy or thiocarbamyl substituent; a urea compound of the formula ##STR4## where each of R' and R" represents a hydrogen atom, a linear or branched alkyl group containing from 1 to 16 carbon atoms, a cycloalkyl group of 6 carbon atoms with or without an alkyl substituent containing from 1 to 3 carbon atoms, or an aryl group with or without at least one alkyl substituent containing from 1 to 6 carbon atoms, and these alkyl, cycloalkyl and aryl groups may further have at least one halogen, aryl, alkenyl, cyano, nitro, alkoxy, phenoxy, thioalkoxy, thiophenoxy, carbalkoxy, carbamate, carbamyl carbaryloxy or thiocarbamyl substituent; a biuret compound of the formula ##STR5## where each of R', R" and R'" has the same meaning as defined for R' and R" in formula (II); and an allophanate compound of the formula ##STR6## where each of R' and R" has the same meaning as defined for R' and R" in formula (II), R 1 represents a linear or branched alkyl group containing from 1 to 16 carbon atoms, a cycloalkyl group of 6 carbon atoms with or without an alkyl substituent containing from 1 to 3 carbon atoms, or an aryl group with or without at least one alkyl substituent containing from 1 to 6 carbon atoms, and these alkyl, cycloalkyl and aryl groups may further have at least one halogen, aryl, alkenyl, nitro, alkoxy, phenoxy or carbamate substituent.
Claim 2
Dependent Claim
442 words
In a process for preparing an aromatic urethane which comprises reacting at temperature in the range of 80°-230° C. pressures in the range of 10-1000 Kg/cm 2 G for a time ranging from 5 minutes to 6 hours an aromatic nitro compound, an organic hydroxyl-containing compound having at least one hydroxyl group, and carbon monoxide in the presence of a catalyst selected from the group consisting of platinum, palladium, rhodium or ruthenium metal or a compound thereof and mixtures thereof and a promoter selected from the group consisting of Lewis acids, Lewis acid-containing compounds and mixtures thereof, the improvement which comprises adding to the reaction system at least one compound selected from the group consisting of an organic primary amino compound of the formula R.sub.o NH.sub.2 ( I) where R o represents a linear or branched alkyl group containing from 1 to 16 carbon atoms, a cycloalkyl group of 6 carbon atoms with or without an alkyl substituent containing from 1 to 3 carbon atoms, or an aryl group with or without at least one alkyl substituent containing from 1 to 6 carbon atoms, and these alkyl, cycloalkyl and aryl groups may further have at least one halogen, aryl, alkenyl, cyano, nitro, alkoxy, phenoxy, thioalkoxy, thiophenoxy, carbalkoxy, carbamate, carbamyl, carbaryloxy or thiocarbamyl substituent; a urea compound of the formula ##STR4## where each of R' and R" represents a hydrogen atom, a linear or branched alkyl group containing from 1 to 16 carbon atoms, a cycloalkyl group of 6 carbon atoms with or without an alkyl substituent containing from 1 to 3 carbon atoms, or an aryl group with or without at least one alkyl substituent containing from 1 to 6 carbon atoms, and these alkyl, cycloalkyl and aryl groups may further have at least one halogen, aryl, alkenyl, cyano, nitro, alkoxy, phenoxy, thioalkoxy, thiophenoxy, carbalkoxy, carbamate, carbamyl carbaryloxy or thiocarbamyl substituent; a biuret compound of the formula ##STR5## where each of R', R" and R'" has the same meaning as defined for R' and R" in formula (II); and an allophanate compound of the formula ##STR6## where each of R' and R" has the same meaning as defined for R' and R" in formula (II), R 1 represents a linear or branched alkyl group containing from 1 to 16 carbon atoms, a cycloalkyl group of 6 carbon atoms with or without an alkyl substituent containing from 1 to 3 carbon atoms, or an aryl group with or without at least one alkyl substituent containing from 1 to 6 carbon atoms, and these alkyl, cycloalkyl and aryl groups may further have at least one halogen, aryl, alkenyl, nitro, alkoxy, phenoxy or carbamate substituent.
Claim 3
Dependent Claim
14 words
The process according to claim 1 wherein said organic primary amino compound is aniline.
Claim 4
Dependent Claim
12 words
The process according to claim 1 wherein said urea compound is urea.
Claim 5
Dependent Claim
13 words
The process according to claim 1 wherein said aromatic nitro compound is nitrobenzene.
Claim 6
Dependent Claim
13 words
The process according to claim 1 wherein said aromatic nitro compound is dinitrotoluene.
Claim 7
Dependent Claim
14 words
The process according to claim 1 wherein said organic hydroxyl-containing compound is ethyl alcohol.
Claim 8
Dependent Claim
14 words
The process according to claim 1 wherein said organic hydroxyl-containing compound is isobutyl alcohol.
Claim 9
Dependent Claim
23 words
The process according to claim 1 wherein said catalyst is elemental palladium, a palladium compound, a palladium compound-containing compound, or a mixture thereof.
Claim 10
Dependent Claim
20 words
The process according to claim 1 wherein said promoter is ferrous chloride, a ferrous chloride-containing compound, or a mixture thereof.
Claim 11
Dependent Claim
20 words
The process according to claim 1 wherein said promoter is ferric chloride, a ferric chloride-containing compound, or a mixture thereof.
Claim 12
Dependent Claim
21 words
The process according to claim 1 wherein said promoter is a complex composed of ferrous chloride and a nitrogen-containing heterocyclic compound.
Claim 13
Dependent Claim
32 words
The process according to claim 11 wherein water is added to the reaction system in an amount equal to from 1 to 100 moles per mole of the starting aromatic nitro compound.
Claim 14
Dependent Claim
375 words
In a process for preparing an aromatic urethane which comprises reacting, at a temperature of 80°-230° C., a and pressure, of 10-1000 Kg/cm 2 G and for a time of from 5 min. to 6 hours an aromatic nitro compound of the formula A--(NO.sub.2)x (V) where A represents a substituted or unsubstituted aromatic residue of an aromatic nitro compound from which the nitro group or groups are removed an x is an integer equal to from 1 to 4, an organic hydroxyl-containing compound of the formula R.sub.1--OH (VI) where R 1 represents a linear or branched alkyl group containing from 1 to 16 carbon atoms, a cycloalkyl group of 6 carbon atoms with or without an alkyl substituent containing from 1 to 3 carbon atoms, or an aryl group with or without at least one alkyl substituent containing from 1 to 6 carbon atoms, and these alkyl, cycloalkyl, and aralkyl groups may further have a halogen, aryl, alkenyl, nitro, alkoxy, phenoxy or carbamate substituent, and carbon monoxide in the presence of a catalyst selected from the group consisting of platinum, palladium, rhodium or ruthenium metal or a compound thereof and mixtures thereof and a promotor selected from the group consisting of Lewis acids, Lewis acid-containing compounds, and mixtures thereof, the improvement which comprises adding to the reaction system at least one compound selected from the group consisting of an aromatic primary amino compound of the formula ##STR7## where A and x have the same meanings as defined in formula (V), R 1 has the same meaning as defined in formula (VI), y is an integer equal to from 1 to 4, z is an integer equal to from 0 to 3, and the sum of y and z does not exceed x; a urea compound of the formula ##STR8## where A' represents a group of the formula ##STR9## and A, R 1 , x, y and z have the same meanings as defined in formula (VII); a biuret compound of the formula ##STR10## where A' has the same meaning as defined in formula (VIII); and an allophanate compound of the formula ##STR11## where A' has the same meaning as defined in formula (VIII) and R 1 has the same meaning as defined in formula (VI).
Claim 15
Dependent Claim
375 words
In a process for preparing an aromatic urethane which comprises reacting, at a temperature of 80°-230° C., a and pressure, of 10-1000 Kg/cm 2 G and for a time of from 5 min. to 6 hours an aromatic nitro compound of the formula A--(NO.sub.2)x (V) where A represents a substituted or unsubstituted aromatic residue of an aromatic nitro compound from which the nitro group or groups are removed an x is an integer equal to from 1 to 4, an organic hydroxyl-containing compound of the formula R.sub.1--OH (VI) where R 1 represents a linear or branched alkyl group containing from 1 to 16 carbon atoms, a cycloalkyl group of 6 carbon atoms with or without an alkyl substituent containing from 1 to 3 carbon atoms, or an aryl group with or without at least one alkyl substituent containing from 1 to 6 carbon atoms, and these alkyl, cycloalkyl, and aralkyl groups may further have a halogen, aryl, alkenyl, nitro, alkoxy, phenoxy or carbamate substituent, and carbon monoxide in the presence of a catalyst selected from the group consisting of platinum, palladium, rhodium or ruthenium metal or a compound thereof and mixtures thereof and a promotor selected from the group consisting of Lewis acids, Lewis acid-containing compounds, and mixtures thereof, the improvement which comprises adding to the reaction system at least one compound selected from the group consisting of an aromatic primary amino compound of the formula ##STR7## where A and x have the same meanings as defined in formula (V), R 1 has the same meaning as defined in formula (VI), y is an integer equal to from 1 to 4, z is an integer equal to from 0 to 3, and the sum of y and z does not exceed x; a urea compound of the formula ##STR8## where A' represents a group of the formula ##STR9## and A, R 1 , x, y and z have the same meanings as defined in formula (VII); a biuret compound of the formula ##STR10## where A' has the same meaning as defined in formula (VIII); and an allophanate compound of the formula ##STR11## where A' has the same meaning as defined in formula (VIII) and R 1 has the same meaning as defined in formula (VI).
Claim 16
Dependent Claim
27 words
The process according to claim 13 wherein A in formula (V) is a phenyl group and R 1 in formula (VI) is an ethyl or isobutyl group.
Claim 17
Dependent Claim
34 words
The process according to claim 13 wherein A in formula (V) is a tolyl group having a nitro, amino or carbamate group and R 1 in formula (VI) is an ethyl or isobutyl group.
Claim 18
Dependent Claim
21 words
The process according to claim 13 wherein said catalyst is elemental palladium, a palladium compound, palladium compound-containing compound, a mixture thereof.
Claim 19
Dependent Claim
20 words
The process according to claim 13 wherein said promoter is ferrous chloride, a ferrous chloride-containing compound, or a mixture thereof.
Claim 20
Dependent Claim
20 words
The process according to claim 13 wherein said promoter is ferric chloride, a ferric chloride-containing compound, or a mixture thereof.
Claim 21
Dependent Claim
21 words
The process according to claim 13 wherein said promoter is a complex composed of ferrous chloride and a nitrogen-containing heterocyclic compound.
Claim 22
Dependent Claim
32 words
the process according to claim 19 wherein water is added to the reaction system in an amount equal to from 1 to 100 moles per mole of the starting aromatic nitro compound.
Claim 23
Dependent Claim
37 words
The process according to claim 20 wherein said catalyst is elemental palladium, a palladium compound, a palladium compound-containing compound, or a mixture thereof and said promoter is a complex of ferrous chloride and a nitrogen-containing heterocyclic compound.
Claim 24
Dependent Claim
44 words
The process according to claim 1 wherein said organic nitro compound is selected from the group consisting of nitro-benzene, o-, m- and p-nitrotoluenes, m- and p-dinitrobenzenes, 2, 4- and 2,6-dinitrotoluenes, bis-(4-nitrophenyl) methane, bis-(4-nitrophenyl) ether, o-, m- and p-chloronitrobenzenes, 2, 3- and 3,4-dichloronitrobenzenes, and 1,5-dinitronaphthalene.
Claim 25
Dependent Claim
33 words
The process according to claim 1 wherein said organic hydroxyl containing compound is selected from the group consisting of methyl alcohol, ethyl alcohol, n- and iso-propyl alcohols, and n-, iso- and tert-butyl alcohols.
Claim 26
Dependent Claim
43 words
The process according to claim 1 wherein said catalyst is selected from the group consisting of elemental palladium; halides, cyanides, thiocyanides, isocyanides, oxides, sulfates, nitrates and carbonyl compounds of palladium; and an addition product or complex of palladium compound with a tertiary amine.
Claim 27
Dependent Claim
37 words
The process according to claim 1 wherein said promotor is selected from the group consisting of ferrous chloride, ferric chloride and the complex thereof with a tertiary amine selected from pyridine, picoline, isoquinoline, quinoline and triethyl amine.
Claim 28
Dependent Claim
53 words
The process according to claim 1 wherein said organic primary amine compound is selected from the group consisting of methylamine, ethylamine, n- and iso-propylamines, butylamine, cyclohexylamine, aniline, o-, m-, and p-diaminobenzenes, 2-amino-4-carbamatetoluene, 4-amino-2-carbamatetoluene, 2-amino-6-carbamatetoluene, o-, m- and p-nitroanilines, 4-nitro-2-aminotoluene, 2-nitro-4-aminotoluene, 2-nitro-6-aminotoluene, 3-nitro-4-aminotoluene, o- and p-phenylenediamines, 2,4- and 2,6-diaminotoluenes, and o-, m- and p-chloroanilines.
Claim 29
Dependent Claim
47 words
The process according to claim 1 wherein R', R" and R'" in formulas (II), (III) and (IV) are independently hydrogen atom, methyl or phenyl, and R 1 in formula (IV) is selected from the group consisting of methyl, ethyl, n- and iso-propyl, and n-, iso- and tert-butyl.
Claim 30
Dependent Claim
148 words
The process according to claim 1 wherein said aromatic compound is nitrobenzene, dinitrobenzene or dinitrotoluene; said organic hydroxyl-containing compound is ethyl alcohol or isobutyl alcohol; said catalyst system is composed of a catalyst selected from elemental palladium, a palladium compound, an addition compound or a complex thereof with a tertiary amine and a mixture thereof and a promotor selected from ferrous chloride, ferric chloride, a complex thereof with prydine, picoline, quinoline, isoquinoline or triethylamine and a mixture thereof; and said compound added to the reaction system is selected from the group consisting of an organic primary amine selected from isopropyl-amine, aniline, 2-amino-4-nitrotoluene, 4-amino-2-nitrotoluene, 2-amino-4-ethylcarbamate toluene and 4-amino-2-ethylcarbamate toluene, a urea compound selected from urea, diphenyl urea and 1-(3-ethylcarbamate-4-methylphenyl)-3-(2-methyl-5-ethylcarbamate-phenyl) urea, a biuret compound formed by heating a mixture of 2,4-toluene diisocyanate and water, and an allophanate compound formed by heating an equimolecular mixture of 2,4-diethylcarbamate toluene and 2,4-diisocyanate toluene.
Claim 31
Dependent Claim
44 words
The process according to claim 13 wherein said catalyst is selected from the group consisting of elemental palladium; halides, cyanides, thiocyanides, isocyanides, oxides, sulfates, nitrates and carbonyl compounds of palladium; and an addition product or complex of a palladium compound with a tertiary amine.
Claim 32
Dependent Claim
37 words
The process according to claim 13 wherein said promotor is selected from the group consisting of ferrous chloride, ferric chloride and the complex thereof with a tertiary amine selected from pyridine, picoline, isoquinoline, quinoline and triethyl amine.
Claim 33
Dependent Claim
29 words
The process according to claim 13 wherein A in formula (V) is selected from the group consisting of phenyl, o-, m- and p-chlorophenyl, and o-, m- and p-tolyl groups.
Claim 34
Dependent Claim
30 words
The process according to claim 13 wherein R 1 in formula (VI) is selected from the group consisting of methyl, ethyl, n- and iso-propyl, and n-, iso- and tert-butyl groups.
Claim 35
Dependent Claim
151 words
The process according to claim 13 wherein said compound of formula (V) is nitrobenzene, dinitrobenzene or dinitrotoluene; and said compound of formula (VI) is an ethyl alcohol or isobutyl alcohol; said catalyst system is composed of a catalyst selected from elemental palladium, a palladium compound, an addition product or a complex thereof with a tertiary amine and a mixture thereof and a promotor selected from ferrous chloride, ferric chloride, a complex thereof with pyridine, picoline, quinoline, isoquinoline or triethylamine and a mixture thereof; and said compound added to the reaction system is selected from the group consisting of an organic primary amine selected from aniline, 2-amino-4-nitrotoluene, 4-amino-2-nitrotoluene, 2-amino-4-ethylcarbamate toluene and 4-amino-2-ethylcarbamate toluene, a urea compound selected from diphenyl urea and 1-(3-ethylcarbamate-4-methylphenyl)-3-(2-methyl-5-ethylcarbamatephenyl) urea, a biuret compound formed by heating a mixture of 2,4-toluene diisocyanate and water, and an allophanate compound formed by heating an equimolecular mixture of 2,4-diethylcarbamate toluene and 2,4-diisocyanate toluene.
Claim 36
Dependent Claim
48 words
The process according to claim 1 wherein said compound added to the reaction system is selected from the group consisting of an organic primary amine selected from isopropylamine, aniline, 2-amino-4-nitrotoluene, 4-amino-2-nitrotoluene, 2-amino-4-ethylcarbamate toluene and 4-amino-2-ethylcarbamate toluene, and a urea compound selected from urea, diphenyl urea and 1-(3-ethylcarbamate-4-methylphenyl)-3-(2-methyl-5-ethylcarbamatephenyl) urea.
Claim 37
Dependent Claim
46 words
The process according to claim 13 wherein said compound added to the reaction system is selected from the group consisting of an organic primary amine selected from aniline, 2-amino-4-nitrotoluene, 4-amino-2-nitrotoluene, 2-amino-4-ethylcarbamate toluene and 4-amino-2-ethylcarbamate toluene, and a urea compound selected from diphenyl urea and 1-(3-ethylcarbamate-4-methylphenyl)-3-(2-methyl-5-ethylcarbamatephenyl) urea.
Claim 38
Dependent Claim
42 words
The process according to claim 13 wherein said aromatic compound is nitrobenzene; said organic hydroxyl-containing compound is ethyl alcohol; said catalyst system is composed of palladium chloride and a ferrous chloride-pyridine complex; and said compound added to the reaction system is aniline.
Claim 39
Dependent Claim
49 words
The process according to claim 13 wherein said aromatic compound is dinitrobenzene; said organic hydroxyl-containing compound is ethyl alcohol; said catalyst system is composed of palladium chloride and a ferrous chloride-pyridine complex; and said compound added to the reaction system is 2-amino-4-ethylcarbamate toluene, 4-amino-2-ethylcarbamate toluene and a mixture thereof.
Claim 40
Dependent Claim
54 words
The process according to claim 13 wherein said aromatic compound is 2,4-dinitrotoluene; said organic hydroxyl-containing compound is ethyl alcohol; said catalyst system is composed of palladium chloride and a ferrous chloride-pyridine complex; and said compound added to the reaction system is 2-amino-4-nitrotoluene, 4-amino-2-nitrotoluene, a mixture thereof, or 2-amino-4-ethylcarbamate toluene, 4-amino-2-ethylcarbamate or a mixture thereof.
References Cited (Backward Citations)
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| 7.5 Years (Year 8) | 1986-12-10 | 1987-06-11 | 1987-12-11 | $3760.00 | Window Closed / Lapsed |
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